Washable coloring composition suitable for use in dry erase markers

ABSTRACT

A washable dry erase coloring composition comprising an acid dye or polymeric dye colorant, a dye vehicle, a release agent, and a dyeblocker additive. The dyeblocker additive is either a sulfonated naphthalene condensation product or a sulfonated phenol-formaldehyde condensation product. The dry erase coloring composition is suitable for use in marking on a whiteboard and enhances fugitivity from skin and fabrics. The dry erase coloring composition may optionally contain a film forming resin. More specifically, the invention is, in one preferred embodiment, a washable erasable whiteboard marker ink comprising an acid dye or polymeric dye, water, a film forming resin, a release agent and a sulfonated phenol-formaldehyde condensation product.

FIELD OF THE INVENTION

The present invention relates generally to the field of washable dryerase coloring compositions for drawing and coloring purposes. In oneparticular aspect, the invention relates to writing instrumentscontaining washable liquid coloring compositions, and more specificallyto the formulations of coloring compositions for use in markers.Further, washable coloring compositions are provided which are suitablefor use on whiteboards.

BACKGROUND OF THE INVENTION

Whiteboards, also known as dry erase boards, are commonly used inoffices, schools, and other locations were a chalkboard might otherwisebe found. Writings on a dry erase board are erasable by wiping lightlywith felt, dry cloth or paper. Suitable whiteboard surfaces generallyinclude a melamine, vinyl, polyethylene laminate, or enamel resin layeraffixed to a backing. Such whiteboards are characterized in that theyhave hard, white surfaces that are very smooth in appearance, and areessentially nonporous. Alternatively, a whiteboard may comprise a sheetof polymeric film such as an acrylic or UV curable resin.

A variety of compositions are known for use in writing on imperviouswriting surfaces such as whiteboards. These coloring compositionssuitable for use on whiteboards must erase easily without requiring acomprehensive cleaning. Additionally, the whiteboard compositions mustbe removable without leaving visible remains commonly termed "ghosting."

Whiteboard coloring compositions suffer from a variety of well knowndeficiencies. Most whiteboard markers are alcohol-based which may betoxic and, thus, are not appropriate for use by young children. Forexample, U.S. Pat. Nos. 4,954,174, 5,316,574, and 5,324,764 describeerasable ink compositions for writing on an impervious surface thatcontain an organic solvent such as an alcohol. Further, many whiteboardmarkers produce writings which are not readily erasable from whiteboardsafter the passage of a significant period of time. Finally, currentwhiteboard markers have a propensity to leave enduring stains onclothing. While permanence is a desirable characteristic of theso-called "permanent" markers, it is one of the most objectionableproperties for coloring instruments used by young children.

Water-based marker compositions have been used. U.S. Pat. Nos. 5,412,021and 5,561,175, for example, describe water-based compositions thatcontain a pigment, a separating agent, and a water-soluble resin. Theseaqueous compositions, however, lack fugitivity from fabrics and skin.

It is therefore one general object of the invention to provide a methodof imparting skin fugitivity to a dry erase coloring composition.

Another object is to provide a dry erase coloring composition which, inaddition to being washable from skin, exhibits enhanced launderabilityfrom fabrics.

A related object is to provide non-toxic, dry erase coloringcompositions, such as inks, which are suitable for use by young childrenwho may make marks on themselves and their clothing.

A further object of the invention is to provide a coloring compositionsuitable for use on whiteboards and other non-porous surfaces which isalso washable from the skin and clothes.

These and other objects and advantages of the present invention, as wellas additional inventive features, will be apparent to those skilled inthe art from the following description of the invention and the appendedclaims.

BRIEF SUMMARY OF THE INVENTION

The discovery of the present invention is that one may incorporate intoa coloring composition a dyeblocker additive which imparts to thecomposition dramatically improved fugitivity from skin. At the sametime, it has been discovered that, in many instances, the dyeblockeradditive will noticeably enhance fugitivity from fabrics ordinarily usedin children's clothing.

In one of its most general aspects, the coloring composition of theinvention comprises a colorant selected from the group consisting of anacid dye and a polymeric dye and a dyeblocker. Suitable dyeblockers arearomatic organic sulfonates and are preferably selected from the groupconsisting of a sulfonated naphthalene condensation product and asulfonated phenol-formaldehyde condensation product. The coloringcompositions of the invention are easily washed from the skin, and, inaddition, are also more easily washed from textiles. In another generalrespect, the present invention includes a method of imparting skinwashability to a dye-containing coloring composition by adding to acoloring composition an effective amount of a dyeblocker selected fromthe group consisting of a sulfonated naphthalene condensation productand a sulfonated phenol-formaldehyde condensation product.

Thus, in one form, the invention is a washable coloring compositioncomprising an acid dye or polymeric dye colorant, a dye vehicle, arelease agent, and a sulfonated phenol-formaldehyde condensation productor a sulfonated naphthalene condensation product. This form of theinvention is suitable for use in marking on a whiteboard. Preferably,the inventive coloring composition also contains a film forming resin.More specifically, the invention is, in one preferred embodiment, anerasable whiteboard marker ink comprising an acid dye or polymeric dyecolorant, water, a film forming resin, a release agent, and a sulfonatedphenol-formaldehyde condensation product. Further, a marker containingthe coloring composition of the invention is provided.

DETAILED DESCRIPTION

The washable coloring composition of the present invention comprises anacid dye or polymeric dye colorant, a dye vehicle, a release agent, anda dyeblocker selected from the group consisting of a sulfonatedphenol-formaldehyde condensation product and a sulfonated naphthalenecondensation product. Preferably, the coloring composition also containsa film forming resin. These washable coloring compositions exhibitenhanced fugitivity from skin and fabrics. This coloring composition issuitable for use for marking on whiteboards and may be easily erased byordinary means with no apparent ghosting.

The dyeblocker components imparts skin fugitivity and, in someinstances, enhanced fabric fugitivity to the coloring compositions ofthe invention. The dyeblocker can be an aromatic organic sulfonate andmore preferably an aromatic organic sulfonate other than an alkylbenzene sulfonate. One group of preferred dyeblockers are sulfonatedphenol-formaldehyde condensation products, sulfonated naphthalenecondensation products, or mixtures thereof. The dyeblockers useful inthe practice of the present invention do not impair the stability of thecoloring compositions of the invention. By stability, it is meant thatthe coloring composition, which includes the condensation productadditive, must not precipitate nor exhibit a marked change in color orpH when maintained at a temperature of 140° F. for two weeks. Inaddition, it is preferred to use dyeblockers which, in addition toimparting fugitivity from skin, also enhance fugitivity from textiles.

Sulfonated phenol-formaldehyde condensation product dyeblockers usefulin the practice of the invention are described in U.S. Pat. No.4,501,591, the disclosure of which is incorporated herein by reference.Suitable sulfonated phenol-formaldehyde condensation products may be,but are not limited to, linear, low molecular weight condensationproducts; that is products having an average molecular weight of lessthan about 1000, for example, in the range of 250 to 700. Such productsare water-soluble and may be prepared by conventional art-recognizedtechniques, for example, by condensation of formaldehyde with one ormore phenols in a mole ratio of about 1.0 to 0.8, phenol(s) toformaldehyde, at a pH of less than 7 using an acid catalyst such as HCl,wherein at least one of the phenols is a phenolsulfonic acid or alkalimetal salt thereof. Preferably, the phenols comprise, in addition to thesulfonic acid or salt thereof, a sulfone, for example, dihydroxyaromatic diphenol sulfone. Such condensation products contain, inaddition to sulfonic acid groups or alkali metal salts thereof, sulfonegroups.

Other sulfonated phenol-formaldehyde condensation products are describedin U.S. Pat. No. 33,365, and U.S. Pat. Nos. 4,592,940 and 4,680,212, thedisclosures of which are incorporated herein by reference.

A sulfonated phenol-formaldehyde condensation product dyeblocker usefulin the present invention is Aerofix N™, commercially available fromAerochem Corporation. Aerofix N is supplied as an aqueous dispersion ofthe phenol-formaldehyde condensation product containing about 17% byweight active condensation product ingredients. Other useful sulfonatedphenol-formaldehyde condensation products are Intratex N™ available fromCrompton and Knowles Corporation (dispersion containing about 18% byweight active condensation product ingredient), and Gascofix NY™available from GCI Technologies, Inc. (dispersion containing about 29%by weight active condensation product ingredient). Compatible mixturesof these sulfonated phenol-formaldehyde condensation products may alsobe used. The sulfonated phenol-formaldehyde condensation product,Aerofix N™, is preferred. Aerofix N™ dramatically enhanced skinwashability and fabric launderability in compositions of the invention.Other sulfonated phenol-formaldehyde condensation products may produceequivalent, or even better, results and are within the scope of theinvention.

A sulfonated naphthalene condensation product dyeblocker useful in thecoloring compositions of the invention is Tamol SN™. Tamol SN™ iscommercially available from Rohm and Haas and supplied in solid formcontaining 100% active ingredient. Other sulfonated naphthalenecondensation products may produce equivalent, or even better, resultsand are within the scope of the invention. The various dyeblockersdiscussed above may be used alone or in combination where thedyeblockers are compatible with each other.

The specific mechanism by which the dyeblocker additive imparts skinfugitivity and enhance fabric fugitivity is not known. However, it isbelieved that the condensation products tie up the reactive sites ofthese substrates, such that the dye used as a colorant in compositionsof the invention has a reduced ability to physically or chemicallyassociate with skin or fabric.

The sulfonated phenol-formaldehyde condensation product Aerofix N™ wastested in numerous water-based dye compositions comprising colorants,preservatives, and humectants. Compositions of the invention shouldcontain a sufficient amount of the sulfonated phenol-formaldehydecondensation product to impart skin fugitivity and enhance fabricfugitivity to the composition.

The amount of dyeblocker additive present in the coloring compositionsof the invention depends upon the specific condensation product used. Ata minimum, the condensation product must be present in an amountsufficient to impart enhanced skin and fabric fugitivity. This effect isseen with as little as about 1% by weight of the active condensationproduct ingredient in the dry erase coloring composition, but is betterstarting at about 3.5% by weight of the active sulfonatedphenol-formaldehyde condensation product ingredient where the dyeblockeradditive is Aerofix N™. In general, a greater amount of condensationproduct additive present in the dry erase coloring composition leads tobetter washability from fabric and skin. However, at a certain point,the addition of more condensation product does not yield any improvementin the washability of the dry erase composition. The upper limit of thedyeblocker additive concentration may also be imposed by constraints onthe viscosity and the long term stability of the composition. Forexample, the dry erase coloring composition cannot have a significantlyviscous consistency or it will not flow through a marker nib.Accordingly, the concentration of condensation product additive ispreferably in the range of from about 2% to about 15% by weight of theactive condensation product ingredient of the total coloringcomposition.

In general, where the Aerofix N™ dispersion is used, the beneficialeffect of the additive occurs at a concentration of at least about 10%by weight of the Aerofix N™ dispersion based on the total coloringcomposition. Where Aerofix N™ is used, the Aerofix N™ component ispreferably present in the range of from about 5% to about 40% by weightof the Aerofix N™ dispersion based on the total coloring composition ofthe invention, and, most preferably, in the range of from about 15% toabout 25% by weight of the Aerofix N™ dispersion based on the totalcoloring composition.

In the coloring compositions of the invention, a colorant is also used.Suitable colorants are dyes which are preferably selected whichotherwise are known to have good launderability from fabrics. When usedin the composition of the invention, such dyes not only enhancewashability from skin, but also enhance launderability from fabric aswell. While certain coloring compositions containing polymeric dyes havebeen removed from skin and fabric with soap and a significant amount ofrubbing, the erasable whiteboard compositions of the present inventioncan be rinsed off using water alone.

One suitable colorant for use in compositions of the present inventionare acid dyes. By way of illustration, and not in limitation, acid dyesthat have been found suitable for use in this invention are Acid Violet12, Acid Green 3, Acid Blue 9, Acid Yellow 17, Acid Yellow 23 and AcidRed 388. Yellow F.D.& C. #6 may also be used.

Another category of suitable colorants (also known as chromophores) foruse in the present invention are polymeric dyes. These colorants arecharacterized as having polymeric chains covalently bonded to achromophore molecule. By way of illustration, and not limitation,polymeric dyes suitable for use in this invention include PalmerScarlet™, Palmer Blue™, Palmer Magenta™, and Experimental Palmer FL RedA 10™. These polymeric dyes are commercially available from MillikenChemical and may be covered by one or more of U.S. Pat. Nos. 4,981,516,5,043,013, and 5,059,244, the disclosures of which are incorporatedherein by reference. Other polymeric dyes useful in the practice of theinvention include polyalkyleneoxy-substituted chromophore compounds suchas, for example, alkyleneoxy-substituted methine colorants.

The inventive coloring compositions may contain either polymeric dyes,acid dyes, or mixtures thereof. Additionally, the compositions maycontain two or more polymeric dyes or two or more acid dyes to achievethe desired color. The colorant is preferably present in an amount offrom about 2% to about 20% by weight of the total coloring compositionof the invention. The minimum concentration of colorant which willproduce a workable coloring composition is governed by the colorintensity desired, though as little as 0.5% colorant may be sufficientfor certain applications. The maximum workable concentration of colorantis determined largely by the ability to maintain a stable composition,and can vary widely depending upon the concentration of othercomponents. It is also a function of the characteristics of the desiredend product, though a practical upper limit in the formulation of thecomposition of the invention as, for example, an erasable whiteboardmarker ink, is about 30% by weight of the total coloring composition ofthe invention since higher concentrations may cause board staining(i.e., ghosting) and an undesirably high viscosity. Preferably, the dryerase coloring composition should have a viscosity less than 6 cps whenused as a dry erase marker ink. For whiteboard applications, too muchdye raises the viscosity and makes it difficult to add a sufficientamount of film forming resin and/or dyeblocker necessary to yield thedesired washability.

The coloring composition of the present invention also contains anamount of an aqueous or other dye vehicle effective to form a dispersionof the remaining components. The preferred dye vehicle is water. Theupper limit of the proportion of water is the amount which will dilutethe composition sufficiently to form a mark having the minimumacceptable visibility on a substrate. The minimum amount of water isthat necessary to disperse the other components and provide acomposition which can be freely dispensed from the selected dispensingelement. Other suitable dye vehicles include alcohol, for example, a 30%denatured alcohol solution. Compatible mixtures of alcohol and water mayalso be used as a dye vehicle. The proportion of dye vehiclecontemplated herein is from about 30% to about 90% by weight of thetotal coloring composition of the invention. Some or all of the watermay be contributed by other components.

The coloring compositions of the invention may also contain a releaseagent. Where the coloring compositions of the invention are to be usedto create marks on a whiteboard, the release agent itself forms aseparating film between the surface of the whiteboard and the filmforming resin. The film forming resin does not form on the surface ofthe board, but instead on top of the release agent. As a result, thefilm forming resin, containing the colorant, may be erased with a drycloth or eraser. Typical release agents include, but are not limited to,siloxanes, such as polydimethylsiloxanes; polyethylene glycols;monobasic higher fatty carboxylic acid esters; mono- or diesters ofdihydric alcohols, wherein the ester has a molecular weight of 100 ormore; fatty acid triglycerides; higher hydrocarbons such as paraffin andsqualene; polyesters and polyethers having molecular weights of 400 ormore; and esters of a polycarboxylic acid with an alcohol.

The preferred release agents are polyalkylene oxide-modifiedpolydimethylsiloxanes sold under the trade name Silwet L-7230™ andSilwet L-7607™ by OSi Specialties, Inc. Other useful release agentsinclude, but are not limited to, Silwet L-7608™ marketed by OSiSpecialties, Inc., DCQ43667™ and FF400™ marketed by Dow Corning,Carbowax™ Polyethylene Glycol 1450 marketed by Union Carbide, andLipopeg 4L™ marketed by Lipo Chemicals Inc. Mixtures of these releaseagents may also utilized in the dry erase coloring compositions of thepresent invention. The release agent contained in the erasablewhiteboard marker ink composition is present in an amount of from about2% to about 30% by weight of the total coloring composition and,preferably, in an amount of from about 5% to about 15% by weight of thetotal coloring composition. At a minimum, the release agent must bepresent in compositions of the invention to be used on whiteboards in anadequate amount to produce compositions that can are easily erasablefrom the whiteboard. However, when excessive amounts of release agentare used, the composition has an excessively high viscosity, which mayrender the composition unsuitable for use in conventional markers.

The coloring compositions of the invention may optionally contain aresin which is water soluble and film forming at room temperature. Whenmarks are formed using the composition of the invention including thisfilm forming resin, and dried on an impervious writing surface, themarks have a continuous resin layer. The water soluble film formingresin also provides the coloring composition with a viscosity suitablefor writing when the composition is used in the form of a whiteboardmarker ink and helps to prevent staining of the whiteboard. It is alsobelieved that the dyeblocker condensation product additives of thepresent invention may also serve as a film-former upon which the dye isdeposited.

The preferred film forming resin for use in the present invention ispolyvinylpyrrolidone sold under the trade name PVP K-15™ by GAFChemicals Corporation. PVP K-15™ is typically supplied in 30% solutionof polyvinylpyrrolidone (i.e., 70% water). Different molecular weightpolyvinylpyrrolidone polymers, such as PVP K-30™, and modifiedpolyvinylpyrrolidone polymers, such as polyvinyl acetate-modifiedpolyvinylpyrrolidone, may also be used. Additional useful film formingresins include, for example, but are not limited to, natural resins,such as gum arabic, rosin, or shellac; modified rosins such as rosinesters, hydrogenated rosins, rosin-modified maleic acid resins orrosin-modified phenol resins; various phenol-resins; cellulosic resinssuch as ethyl cellulose resins or acetyl cellulose resins; ketoneresins, polyvinyl alcohol, polyvinyl acetate resins, petroleum resins,polyvinyl butyral resins, vinylpyrrolidone-vinyl acetate copolymerresins or polyacrylic acid ester resins. Mixtures of two or more ofthese film forming resins may also be employed in the present invention.

The film forming resin should be used in an effective amount.Preferably, the film forming resin is contained in the coloringcomposition suitable for use on whiteboards is present in an amount offrom about 0% to about 10% by weight of the active film forming resinadded of the total coloring composition and, preferably, in an amount offrom about 1% to about 5% by weight of the active film forming resinbased on the total composition of the coloring composition of theinvention. Where the film forming resin used is the polyvinylpyrrolidonesupplied in solution as PVP K-15™, from about 0% to about 30% by weightof the PVP K-15™ solution based on the total weight of the coloringcomposition may be used and, preferably, from about 5% to about 15% byweight of the PVP K-15™ solution is used based on the total weight ofthe coloring composition. The actual amount of film forming resin addedto the coloring compositions of the invention depends upon theparticular colorant used. When the amount of film forming resin is toolarge, the resultant dry erase coloring composition has an excessivelyhigh viscosity so that it writes poorly and, moreover, the writingsformed therewith are not readily erased from a whiteboard.

The inventive dry erase coloring composition can be used as an erasablewhiteboard marker ink in which the dye vehicle is water. The erasablewhiteboard marker ink can be supplied in a delivery system, such as amarking instrument, to enable children to color or draw on impervioussurfaces such as whiteboards. Suitable nibs for use in such a system arebonded fiber or sintered plastic nibs.

Also provided in the instant invention is a marking pen containing thecoloring composition of the invention in the form of an ink. The markingpen generally may use any conventional marker. Preferably, the markerbarrel uses a bonded fiber or sintered plastic nib. The marker reservoircontaining the ink can be any standard marker delivery system including,but not limited to, acetate, polyester, or polypropylene fiber systemsor a fiberless system may be used.

In a preferred embodiment of invention, the coloring composition of theinvention is in the form of an erasable whiteboard marker ink. The inkcontains a colorant, water, a release agent, a film forming resin, and adyeblocker additive selected from a sulfonated naphthalene condensationproduct, a sulfonated phenol-formaldehyde condensation product, andmixtures thereof. This inventive whiteboard marker ink exhibitsfavorable dry erase characteristics and lacks ghosting on mostwhiteboards. The fugitivity of this whiteboard marker ink from skin andfabric is also excellent.

Compositions of the present invention may, when in the form of anerasable whiteboard marker ink, also advantageously include a humectant,a surfactant, a preservative, a defoamer, and/or a pH regulant. Thesematerials and their functions are well known, and their mention here isby way of illustration only. Generally, any effective amount of theadditive may be used so long as the stability of the coloringcomposition is not adversely affected and the composition is suitablefor use in the desired end product.

For example, it may be possible to include a humectant in an erasablewhiteboard marker ink to retard the evaporation of water from the inksolution. This avoids unduly rapid drying of the ink in the marker nibwhich can cause clogging of the nib and impair the function of themarker. Further, a humectant may improve freeze/thaw stability of theinventive ink compositions. Typical humectants include polyhydricalcohols such as glycerine, propylene glycol, ethylene glycol, anddiethylene glycol, hydroxylated starches, low molecular weight(m.w.=200-400) poly(ethylene glycols), and mixtures of these materials.Any effective amount of humectant may be used although a generallyuseful concentration range for these humectants is from about 5% up toabout 30% by weight of the total coloring composition.

Surfactants in any effective amount (generally up to about 0.1% byweight) are also useful in the preferred marker ink or erasablewhiteboard marker ink compositions of the invention for the purpose ofadjusting such properties as viscosity (for proper dispensing of inkthrough the nib), and surface tension (for good flow properties andwhiteboard wetting). Nonionic surfactants, such as poly (ethyleneglycol) ether, alkylaryl polyether alcohol, fluorinated alkyl esters,and mixtures of such materials are preferred for use in marker inks orerasable whiteboard marker inks.

Preservatives of conventional types are also advantageously employed inthe compositions of the invention when used as an erasable whiteboardmarker ink to extend the shelf life of the composition. The preservativepreferably serves as both a bactericide and a fungicide. Some typicalpreservatives useful in the present invention include methylp-hydroxybenzoate, glutaraldehyde, hydroxybenzoic acid esters,3-iodo-2-propynyl butyl carbamate, bicyclic oxazolidones, and a biocidecomprising as the active ingredients5-chloro-2-methyl-4-isothiazolin-3-one and,2-methyl-4-isothiazolin-3-one.

Preservatives are usually effective when present in any effective amountbut generally are present in amounts of from about 0.1% up to about 1%by weight. Preferred preservatives include Kathon PFM™(isothiazolinones) manufactured by Rohm and Haas, and Nuosept 95™(bicyclic oxazolidines solutions) manufactured by Huls America.

The pH of the coloring compositions of the present invention ispreferably in the range of about 7.0 to 9.0, more preferably about 8.0to 8.5. To maintain this basic pH, a pH regulant may be employed.Preferably, neutralized versene is used as a pH regulant. In addition tocontrolling pH, neutralized versene may also help ease the erasabilityof some dyes from whiteboards when compositions of the invention areused as whiteboard marker inks. The pH regulant may be added in anamount ranging from about 0% to about 20% by weight. In one preferredcomposition, the pH regulant, neutralized versene, is added in an amountof about 10% by weight of the total erasable whiteboard marker inkcomposition.

Additionally, the coloring compositions of the present invention mayalso contain a defoamer to prevent foaming during mixture of the variouscomponents. Suitable defoamers include silicones and siloxanes. Thepreferred defoamer is Tego Foamax 800™ marketed by Goldschmidt ChemicalCorp. Other suitable defoamers include Zerofome AF-200™ marketed byNuTech Corp, Surfynol DF58™ marketed by Air Products, and Foamaster H™marketed by Henkel. The addition of defoamer to the coloringcompositions of the present invention does not adversely affect theremovability of these compositions from whiteboards when thecompositions are used as whiteboard marker inks. The amount of defoamerdepends upon the amounts of other components present in the coloringcomposition, although typically about 0.1% to about 5% by weight of thetotal coloring composition is used.

EXAMPLES

Examples of coloring compositions of the present invention are asfollows. These examples further illustrate the present invention but, ofcourse, should not be construed as in any way limiting its scope.Quantities are in percent by weight of the total composition. Theseexample compositions are suitable for use in marking on whiteboards.

Different coloring compositions were prepared using acid and polymericdyes and a dyeblocker condensation product additive. These compositionswere formulated in the form of marker inks. These compositionscontaining a film forming resin, a release agent, and dyeblockercondensation product additive are set forth below in Examples 1-8. Inexamples 1-2 and 4-8, the dyeblocker additive is the sulfonatedphenol-formaldehyde condensation product, Aerofix N™. In example 3, thedyeblocker additive is the sulfonated naphthalene condensation product,Tamol SN™.

Example 1--Red

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         52.54                                                   (dye vehicle)                                                                 Palmer Scarlet                     9.99                                       (polymeric dye)                                                               Palmer FL Red A1O                  2.00                                       (polymeric dye)                                                               Aerofix N                          19.97                                      (phenol-formaldehyde condensation product)                                    PVP K-30 (30% solution)            5.14                                       (film forming resin)                                                          Silwet L-7607                      9.99                                       (release agent)                                                               Nuosept 95                         0.30                                       (preservative)                                                                Kathon PFM                         0.08                                       (preservative)                                                              ______________________________________                                    

Example 2--Blue

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         44.62                                                   (dye vehicle)                                                                 Palmer Blue                        5.00                                       (polymeric dye)                                                               Aerofix N                          20.00                                      (phenol-formaldehyde condensation product)                                    PVP K-15 (30% solution)            10.00                                      (film forming resin)                                                          Silwet L-7607                      10.00                                      (release agent)                                                               Neutralized versene                10.00                                      (pH regulant)                                                                 Nuosept 95                         0.30                                       (preservative)                                                                Kathon PFM                         0.08                                       (preservative)                                                              ______________________________________                                    

Example 3--Yellow

    ______________________________________                                        Component            wt. %                                                    ______________________________________                                        Deionized water      72.62                                                      (dye vehicle)                                                                 Acid Yellow 23                     2.00                                       (acid dye)                                                                    Tamol SN                           5.00                                       (naphthalene condensation product)                                            PVP K-15 (30% solution)           10.00                                       (film forming resin)                                                          Silwet L-7607                     10.00                                       (release agent)                                                               Nuosept 95                         0.30                                       (preservative)                                                                Kathon PFM                         0.08                                       (preservative)                                                              ______________________________________                                    

Example 4--Green

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         55.62                                                   (dye vehicle)                                                                 Palmer Blue                         3.20                                      (polymeric dye)                                                               Acid Yellow 23                      0.80                                      (acid dye)                                                                    Aerofix N                          20.00                                      (phenol-formaldehyde condensation product)                                    PVP K-15 (30% solution)            10.00                                      (film forming resin)                                                          Silwet L-7607                      10.00                                      (release agent)                                                               Nuosept 95                          0.30                                      (preservative)                                                                Kathon PFM                          0.08                                      (preservative)                                                              ______________________________________                                    

Example 5--Black

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         39.82                                                   (dye vehicle)                                                                 Palmer Blue                        4.40                                       (polymeric dye)                                                               Palmer Magenta                     4.40                                       (polymeric dye)                                                               FD&C Yellow #6                 1.00                                           (acid dye)                                                                    Aerofix N                         20.00                                       (phenol-formaldehyde condensation product)                                    PVP K-15 (30% solution)           10.00                                       (film forming resin)                                                          Silwet L-7607                     10.00                                       (release agent)                                                               Neutralized versene               10.00                                       (pH regulant)                                                                 Nuosept 95                         0.30                                       (preservative)                                                                Kathon PFM                         0.08                                       (preservative)                                                              ______________________________________                                    

Example 6--Orange

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         56.62                                                   (dye vehicle)                                                                 FD&C Yellow #6                  3.00                                          (acid dye)                                                                    Aerofix N                          20.00                                      (phenol-formaldehyde condensation product)                                    PVP K-15 (30% solution)            10.00                                      (film forming resin)                                                          Silwet L-7607                      10.00                                      (release agent)                                                               Nuosept 95                          0.30                                      (preservative)                                                                Kathon PFM                          0.08                                      (preservative)                                                              ______________________________________                                    

Example 7--Violet

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         46.42                                                   (dye vehicle)                                                                 Palmer Magenta                     3.20                                       (polymeric dye)                                                               Aerofix N                         20.00                                       (phenol-formaldehyde condensation product)                                    PVP K-15 (30% solution)           10.00                                       (film forming resin)                                                          Silwet L-7607                     10.00                                       (release agent)                                                               Neutralized versene               10.00                                       (pH regulant)                                                                 Nuosept 95                         0.30                                       (preservative)                                                                Kathon PFM                         0.08                                       (preservative)                                                              ______________________________________                                    

Example 8 --Brown

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         42.06                                                   (dye vehicle)                                                                 Palmer Blue                          0.88                                     (polymeric dye)                                                               FD&C Yellow #6                   1.00                                         (acid dye)                                                                    Palmer Scarlet                       5.68                                     (polymeric dye)                                                               Aerofix N                           20.00                                     (phenol-formaldehyde condensation product)                                    PVP K-15 (30% solution)             10.00                                     (film forming resin)                                                          Silwet L-7607                       10.00                                     (release agent)                                                               Neutralized versene                 10.00                                     (pH regulant)                                                                 Nuosept 95                           0.30                                     (preservative)                                                                Kathon PFM                           0.08                                     (preservative)                                                              ______________________________________                                    

TEST PROCEDURES 1. Skin Fugitivity

The fugitivity from skin of the compositions of the invention wasmeasured by the following test:

1. Wash hands with soap and warm water. The pre-stain cleansing removesexcess oil and dirt from the skin and provides a more consistent skinsurface for testing. Allow the skin to dry for 30 seconds.

2. With the compositions of the invention used in a marker having asintered plastic nib, draw a stripe on the palm of the hand with theflat side of the nib. In the usual case, a 1/4 inch wide by 1 inch longstripe works well. Apply enough pressure and/or multiple passes todevelop a stripe with good color intensity. If it is desired to make acomparison among two or more compositions, more than one stripe may bedrawn. Let stripes dry for fifteen minutes.

3. In the case of a marker, place hand under tap and briefly rinse offexcess ink with warm water.

4. Wash hands with Ivory brand bar soap in the following manner: latherusing a minimum amount of soap; replace soap in soap dish; rub handstogether briskly with modest pressure for 30 seconds; rinse away soap.

5. Wipe hands dry with paper towels, and complete the drying with arelatively dry towel. A dry towel will help to rub off residual tracesof ink.

2. Fabric Fugitivity

The fugitivity from fabric of the compositions of the invention wasmeasured by the following test.

1. Pre-wash test fabrics with bleach, non-staining water softener andordinary household phosphate detergent powder using 120° F. hot water asdirected in ASTM D4265-83, and dry.

2. Cut test swatches of pre-washed fabrics to be tested.

3. Deposit marker inks onto fabric swatches and allow to dry for 4hours.

4. Staple a group of stained swatches to the edges of a bath towel.

5. Add a dummy load of unstained fabrics to provide a four pound washload. Wash the load in a washing machine for 12 minutes with a warm(about 80° F. to about 90° F.)/cold cycle or a cold (about 35° F. toabout 55° F.)/cold cycle.

6. Dry the load in a dryer.

7. Detach the test swatches from the carrier towel, iron, and observedegree of staining.

EVALUATION OF TEST DATA

Skin and fabric fugitivity data are based on a visual rating system asfollows:

0=no stain (rinse with soap and water)

0*=no stain (water rinse only for 30 seconds)

0.5=very light stain (rinse with soap and water)

0.5*=very light stain (water rinse only for 30 seconds)

1=light stain

2=light to moderate stain

3=moderate to heavy stain

4=heavy stain

The viscosity, pH and skin fugitivity of the coloring compositions inExamples 1-8 is set forth in Table I. Skin fugitivity was measured on 14individuals. As washability results will vary by individual, the rangeof observed skin fugitivity for each of the coloring compositionsexamples is provided.

                  TABLE I                                                         ______________________________________                                        Skin Fugitivity                                                                 Example      viscosity                                                        Number         (cps)            pH      Skin Fugitivity                     ______________________________________                                        1          5.33     8.20       0, 0*, 0.5*                                      2              4.17             7.95     0, 0*, 0.5, 0.5*, 1                  3              3.17             7.50     0, 0.5, 0.5*                         4              3.76             8.05     0, 0*                                5              5.56             8.00     0, 0*                                6              4.05             8.40     0, 0*, 0.5, 0.5*                     7              4.57             8.19     0, 0*, 0.5*                          8              5.25             8.15     0, 0*                              ______________________________________                                    

The fabric fugitivity data of the coloring compositions in Examples 1-8is set forth in Table II. The washability of these inks was tested on50% cotton/50% polyester blends and 100% cotton. Additionally,washability was examined using a washing machine with both a cold/coldcycle and a warm/cold cycle. The cold/cold cycle was repeated on thefabric samples. As demonstrated, no stains were observed on either the50% cotton/50% polyester blend or the 100% cotton samples after a secondcold wash. For comparison, the fugitivity from fabric of a controlcoloring composition was analyzed. The control is a typicalalcohol-based whiteboard ink composition.

                  TABLE II                                                        ______________________________________                                        Fabric Fugitivity                                                                       Ex     Ex    Ex   Ex  Ex  Ex  Ex   Ex                                 1 2 3 4 5 6 7 8 Cntrl                                                       ______________________________________                                        50%/50% Blend                                                                           1.5    0     1    1   1   0.5 0.5  0.5 4                              (lst cold cycle)                                                              50%/5O% Blend    0    0    0    0    0    0    0    0    3.5                  (2nd cold cycle)                                                              100% Cotton      2    0    1    1    1.5  0.5  1.5  1    4                    (1st cold cycle)                                                              100% Cotton      0.5  0    0    0    0    0    0    0    3.5                  (2nd cold cycle)                                                              50%/50% Blend    0    0    0    0    0    0    0    0    4                    (warm cycle)                                                                  100% Cotton      0    0    0    0    0    0    0    0    4                    (warm cycle)                                                                ______________________________________                                    

From the foregoing description and examples, it can be seen that thecoloring compositions of the present invention containing a dyeblockerexhibit enhanced fugitivity from skin and fabric.

Coloring compositions of the invention containing a dyeblockercondensation product additive other than Aerofix N are set forth belowin Examples 9-12. Examples 13-16 below illustrate coloring compositionsof the invention that do not contain a film forming resin. Each of theseexamples is in the form of a marker ink.

Example

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         69.62                                                   (dye vehicle)                                                                 Palmer Blue                        5.00                                       (polymeric dye)                                                               Intratex N                         5.00                                       (phenol-formaldehyde condensation product)                                    PVP K-15 (30% solution)           10.00                                       (film forming resin)                                                          Silwet L-7607                     10.00                                       (release agent)                                                               Nuosept 95                         0.30                                       (preservative)                                                                Kathon PFM                         0.08                                       (preservative)                                                              ______________________________________                                    

Example

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         66.37                                                   (dye vehicle)                                                                 Acid Blue 9                          1.25                                     (acid dye)                                                                    Gascofix NY                         12.00                                     (phenol-formaldehyde condensation product)                                    PVP K-15 (30% solution)             10.00                                     (film forming resin)                                                          Silwet L-7607                       10.00                                     (release agent)                                                               Nuosept 95                           0.30                                     (preservative)                                                                Kathon PFM                           0.08                                     (preservative)                                                              ______________________________________                                    

Example

    ______________________________________                                        Component            wt. %                                                    ______________________________________                                        Deionized water      72.62                                                      (dye vehicle)                                                                 Acid Yellow 23                     2.00                                       (acid dye)                                                                    Tamol SN                           5.00                                       (naphthalene condensation product)                                            PVP K-15 (30% solution)           10.00                                       (film forming resin)                                                          Silwet L-7607                     10.00                                       (release agent)                                                               Nuosept 95                         0.30                                       (preservative)                                                                Kathon PFM                         0.08                                       (preservative)                                                              ______________________________________                                    

Example

    ______________________________________                                        Component            wt. %                                                    ______________________________________                                        Deionized water      54.82                                                      (dye vehicle)                                                                 Palmer Blue                          4.40                                     (polymeric dye)                                                               Palmer Magenta                       4.40                                     (polymeric dye)                                                               FD&C Yellow #6                   1.00                                         (acid dye)                                                                    Tamol SN                             5.00                                     (naphthalene condensation product)                                            PVP K-15 (30% solution)             10.00                                     (film forming resin)                                                          Neutralized versene                 10.00                                     (pH regulant)                                                                 Silwet L-7607                       10.00                                     (release agent)                                                               Nuosept 95                           0.30                                     (preservative)                                                                Kathon PFM                           0.08                                     (preservative)                                                              ______________________________________                                    

Example

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         52.02                                                   (dye vehicle)                                                                 Palmer Blue                         0.90                                      (polymeric dye)                                                               Palmer Scarlet                      5.70                                      (polymeric dye)                                                               FD&C Yellow #6                  1.00                                          (acid dye)                                                                    Aerofix N                          20.00                                      (phenol-formaldehyde condensation product)                                    Silwet L-7607                      10.00                                      (release agent)                                                               Neutralized versene                10.00                                      (pH regulant)                                                                 Nuosept 95                          0.30                                      (preservative)                                                                Kathon PFM                          0.08                                      (preservative)                                                              ______________________________________                                    

Example

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         49.82                                                   (dye vehicle)                                                                 Palmer Blue                         4.40                                      (polymeric dye)                                                               FD&C Yellow #6                  1.00                                          (acid dye)                                                                    Palmer Magenta                      4.40                                      (polymeric dye)                                                               Aerofix N                          20.00                                      (phenol-formaldehyde condensation product)                                    Silwet L-7607                      10.00                                      (release agent)                                                               Neutralized versene                10.00                                      (pH regulant)                                                                 Nuosept 95                          0.30                                      (preservative)                                                                Kathon PFM                          0.08                                      (preservative)                                                              ______________________________________                                    

Example

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         54.62                                                   (dye vehicle)                                                                 Palmer Blue                         5.00                                      (polymeric dye)                                                               Aerofix N                          20.00                                      (phenol-formaldehyde condensation product)                                    Silwet L-7607                      10.00                                      (release agent)                                                               Neutralized versene                10.00                                      (pH regulant)                                                                 Nuosept 95                          0.30                                      (preservative)                                                                Kathon PFM                          0.08                                      (preservative)                                                              ______________________________________                                    

Example

    ______________________________________                                        Component               wt. %                                                 ______________________________________                                        Deionized water         66.62                                                   (dye vehicle)                                                                 FD&C Yellow #6                3.00                                            (acid dye)                                                                    Aerofix N                         20.00                                       (phenol-formaldehyde condensation product)                                    Silwet L-7607                     10.00                                       (release agent)                                                               Nuosept 95                        0.30                                        (preservative)                                                                Kathon PFM                        0.08                                        (preservative)                                                              ______________________________________                                    

All of the references cited herein, including patents, patentapplications, and publications, are hereby incorporated in theirentireties by reference.

While this invention has been described with an emphasis upon preferredembodiments, it will be obvious to those of ordinary skill in the artthat variations of the preferred embodiments may be used and that it isintended that the invention may be practiced otherwise than asspecifically described herein. Accordingly, this invention includes allmodifications encompassed within the spirit and scope of the inventionas defined by the following claims.

What is claimed is:
 1. A washable coloring composition comprising:(a)one or more colorants selected from the group consisting of an acid dye,a polymeric dye, and mixtures thereof; (b) a dye vehicle; (c) a filmforming resin; (d) a release agent; and (e) a dyeblocker in an amountsufficient to enhance the fugitivity of said composition from skin andfabric.
 2. The washable coloring composition according to claim 1,wherein said dyeblocker is selected from the group consisting of asulfonated naphthalene condensation product, a sulfonatedphenol-formaldehyde condensation product, and mixtures thereof.
 3. Thewashable coloring composition according to claim 2, wherein saiddyeblocker is a sulfonated naphthalene condensation product.
 4. Thewashable coloring composition according to claim 2, wherein saiddyeblocker is a sulfonated phenol-formaldehyde condensation product. 5.The washable coloring composition according to claim 1, wherein said oneor more colorants is a polymeric dye.
 6. The washable coloringcomposition according to claim 1, wherein said coloring composition issuitable for use on whiteboards.
 7. The washable coloring compositionaccording to claim 1, wherein said dye vehicle is water.
 8. The washablecoloring composition according to claim 1, further comprising apreservative.
 9. The washable coloring composition according to claim 8,wherein said preservative is selected from the group consisting ofmethyl p-hydroxybenzoate, glutaraldehyde, hydroxybenzoic acid esters,3-iodo-2-propynyl butyl carbamate, bicyclic oxazolidones, a biocidecomprising as the active ingredients5-chloro-2-methyl-4-isothiazolin-3-one and,2-methyl-4-isothiazolin-3-one, and mixtures thereof.
 10. An erasablewhiteboard marker ink comprising:(a) one or more colorants selected fromthe group consisting of an acid dye, a polymeric dye, and mixturesthereof; (b) water; (c) a film forming resin; (d) a release agent; and(e) a dyeblocker selected from the group consisting of a sulfonatednaphthalene condensation product, a sulfonated phenol-formaldehydecondensation product, and mixtures thereof in an amount sufficient toenhance the fugitivity of said composition from skin and fabric.
 11. Anerasable whiteboard marker ink according to claim 10, wherein said oneor more colorants is an acid dye.
 12. An erasable whiteboard marker inkaccording to claim 10, wherein said one or more colorants is a polymericdye.
 13. An erasable whiteboard marker ink according to claim 10,wherein said dyeblocker is a sulfonated naphthalene condensationproduct.
 14. An erasable whiteboard marker ink according to claim 10,wherein said dyeblocker is a sulfonated phenol-formaldehyde condensationproduct.
 15. An erasable whiteboard marker comprising a marker barrel,an ink and a nib, said ink comprising:(a) one or more colorants selectedfrom the group consisting of an acid dye, a polymeric dye, and mixturesthereof; (b) water; (c) a film forming resin; (d) a release agent; and(e) a dyeblocker selected from the group consisting of a sulfonatednaphthalene condensation product, a sulfonated phenol-formaldehydecondensation product, and mixtures thereof in an amount sufficient toenhance the fugitivity of said composition from skin and fabric.
 16. Anerasable whiteboard marker according to claim 15, wherein said one ormore colorants is an acid dye.
 17. An erasable whiteboard markeraccording to claim 15, wherein said one or more colorants is a polymericdye.
 18. An erasable whiteboard marker according to claim 15, whereinsaid dyeblocker is a sulfonated naphthalene condensation product.
 19. Anerasable whiteboard marker according to claim 15, wherein saiddyeblocker is a sulfonated phenol-formaldehyde condensation product. 20.An erasable whiteboard marker according to claim 15, wherein said nib isselected from the group consisting of bonded fiber nibs and sinteredplastic nibs.
 21. An aqueous erasable whiteboard ink compositionsuitable for use in a marking instrument, said compositioncomprising:(a) one or more colorants selected from the group consistingof an acid dye, a polymeric dye, and mixtures thereof; (b) a filmforming resin in an amount of from about 1% to about 10% by weight ofactive film forming resin of the total composition; (c) a release agentin an amount of from about 2% to about 30% by weight of the totalcomposition; (d) a preservative in an amount of from about 0.1% to about1% by weight of the total composition; (e) a sulfonatedphenol-formaldehyde condensation product in an amount of from about 2%to about 15% by weight of total composition.
 22. A method of impartingskin and fabric fugitivity to a dry erase coloring compositioncontaining an acid dye or polymeric dye, comprising adding to saidcomposition a dyeblocker selected from the group consisting of asulfonated naphthalene condensation product, a sulfonatedphenol-formaldehyde condensation product, and mixtures thereof in anamount sufficient to enhance the fugitivity of said composition fromskin and fabric.
 23. A washable dry erase coloring compositioncomprising:(a) one or more colorants selected from the group consistingof an acid dye, a polymeric dye, and mixtures thereof; (b) a dyevehicle; (c) a release agent; and (d) a dyeblocker selected from thegroup consisting of a sulfonated naphthalene condensation product, asulfonated phenol-formaldehyde condensation product, and mixturesthereof in an amount sufficient to enhance the fugitivity of saidcomposition from skin and fabric.
 24. The washable dry erase coloringcomposition according to claim 23, further comprising a film formingresin.
 25. The washable dry erase coloring composition according toclaim 23, wherein said one or more colorants is an acid dye.
 26. Thewashable dry erase coloring composition according to claim 23, whereinsaid one or more colorants is a polymeric dye.
 27. The washable dryerase coloring composition according to claim 23, wherein saiddyeblocker is a sulfonated naphthalene condensation product.
 28. Thewashable dry erase coloring composition according to claim 23, whereinsaid dyeblocker is a sulfonated phenol-formaldehyde condensationproduct.
 29. An erasable whiteboard marker ink comprising:(a) one ormore colorants selected from the group consisting of an acid dye, apolymeric dye, and mixtures thereof; (b) a dye vehicle; (c) a releaseagent; and (d) a dyeblocker selected from the group consisting of asulfonated naphthalene condensation product, a sulfonatedphenol-formaldehyde condensation product, and mixtures thereof in anamount sufficient to enhance the fugitivity of said composition fromskin and fabric.
 30. An erasable whiteboard marker ink according toclaim 29, wherein said dyeblocker is a sulfonated naphthalenecondensation product.
 31. An erasable whiteboard marker ink according toclaim 29, wherein said dyeblocker is a sulfonated phenol-formaldehydecondensation product.